Relative particle size distribution of plutonium polymer colloid and its aging effective were determined by using an ultracentrifuge. The distribution is not uniform. In the early stage of polymerization, very fine polymer particles of plutonium are formed. The fraction of the larger particles increases with aging.
Thermal behaviour of hexaamminenickel(II) nitrate and tris(ethylenediamine)nickel(II) nitrate have been investigated by means of simultaneous thermogravimetry/DTA coupled online with mass spectral (MS) studies and temperature resolved X-ray diffraction (TR-XRD) techniques under inert atmospheric condition. Both the complexes produce highly exothermic reactions during heating due to the oxidation of the evolved ammonia or ethylenediamine by the decomposition products of Ni(NO3)2. Evolved gas analysis by MS studies detected fragments like NH2 and NH ions with weak intensity. The decomposition of nitrate group generates N, N2, NO, O2 and N2O species. Ethylenediamine (m/z 60) is fragmented to H2 (m/z 2), N (m/z 14), NH3 (m/z 17) and CH2=CH2/N2 (m/z 28) species. The formation of the intermediates was monitored by in situ TR-XRD. The residue of thermal decomposition for both the complexes was found to be crystalline NiO in the nano range.
Detailed investigation on the thermal behaviour of hexaamminenickel(II) chloride and hexaamminenickel(II) bromide has been carried out by means of simultaneous TG/DTA coupled online with mass spectroscopy (TG-MS) and temperature-resolved X-ray diffraction (TR-XRD). Evolved gas analyses by TG-MS revealed the presence of NH2, NH, N2 and H2 fragments in addition to ammonia during the deamination process. These transient species resulted due to the fragmentation of the evolved ammonia during pyrolysis. The intermediates formed during the thermal deamination stages were monitored by in situ TR-XRD. The final product of the decomposition was found to be nano size metallic nickel in both cases. Morphology of the complexes, intermediates and the residue formed at various decomposition stages was analysed by scanning electron microscope (SEM). Kinetic analyses using isoconversional method for deamination and dehalogenation reaction show that the activation energies vary with the extent of conversion, indicating the multi-step nature of these solid state decomposition reactions.
Authors:Y. Minai, T. Fukushima, S. Ogasawara, M. Ichikawa, and T. Tominaga
Fe-57 Mössbauer spectra of silica-supported Pd–Fe bimetallic catalysts show remarkable changes with varying Fe/Pd atomic ratios. From the spectra, the main Fe-component is estimated as highly dispersed Fe in the Fe/Pd range of 0.05–0.3 and -Fe ensemble and Fe–Pd intermetallics in the Fe/Pd range above 0.3. It is suggested that the chemical state of iron is associated with the catalytic performance in effective CO–H2 conversion to methanol.
Authors:Y. Minai, T. Fukushima, M. Ichikawa, and T. Tominaga
Silica supported Rh–Fe catalysts were characterized by means of in situ57Fe Mössbauer spectroscopy. The Mössbauer spectra indicated that iron on the silica support existed either as Fe/O/ in the Rh–Fe alloy or as Fe3+ in Rh–Fe metal cluster compounds. The (Fe3+/Fe/O/) ratio and Mössbauer parameters were found to depend on the (Fe/Rh) atomic ratio in the catalysts. Such dependence corresponded to the change of catalytic properties of the supported Rh–Fe catalyst with the varying (Fe/Rh) ratio.
Authors:T. Nozaki, M. Ichikawa, T. Sasuga, and M. Inarida
Uranium in human bone, drinking water and daily diet has been determined by neutron activation analysis using the238U(n, γ)239U reaction. An improved scheme for the separation of the239U is proposed; with this scheme, after neutron irradiation in a 100 kW TRIGA reactor, a uranium content as low as 5·10−11 g can be determined reliably, rapidly and easily. A wide range of uranium concentrations, from about 0.1 ppb up to about
10 ppb has been found in the bones of normal Japanese. Water from several Japanese city water services, and the daily diet
taken in two Japanese cities, have been found to contain an average 9·10−9 g/l and 1.5 μg per person-day uranium, respectively.
Authors:S. Usuda, N. Shinohara, H. Yoshikawa, S. Ichikawa, and T. Suzuki
Anion exchange separation of250Fm (30 m) synthesized by the12C+242Pu and16O+238U reactions has been investigated with mineral acid-methyl alcohol mixed media at elevated temperature. Fermium was chromatographically separated from the other transplutonium elements, the target materials and an Al catcher foil by anion exchange with mixtures of nitric acid and methyl alcohol. By use of the mixed media of hydrochloric acid and methyl alcohol, Fm together with Cf was separated from Al, Am, Cm, Pu, U and major fission products. The separation systems are suitable for rapid separation and immediate alpha-counting source preparation of Fm.
Authors:H. Natsume, H. Umezawa, T. Suzuki, F. Ichikawa, T. Sato, S. Baba, and H. Amano
A scheme for the sequential separation of fission products has been developed on the basis of ion-exchange techniques. It
consists of a main cation-exchange process for group separation and subsidiary processes of cation or anion exchange for further
separations or purifications of the individual fission products. By the present method, Zn, Rb, Sr, Y, (Zr), Mo, Pd, Cd, Te,
Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu and Tb can be separated simultaneously from an irradiated uranium sample. Of these, alkali,
alkaline earth and rare earth metal ions are separated quantitatively. A polarographic method was applied to determine the
recoveries of Zn, Mo, Pd, Cd and Te, which were not separated quantitatively.
Authors:M. Tanaka, Y. Sakai, T. Tominaga, A. Fukuoka, T. Kimura, and M. Ichikawa
Phthalocyanineiron/II/ in NaY zeolite was synthesized via various processes from an iron carbonyl compound into NaY zeolite in gaseous phase. Mössbauer spectra of the final product /phthalocyanineiron/II// and the precursor species /iron oxide and [phthalocyaninato/2-/]bis/pyridine/iron/II// in NaY zeolite were measured to characterize the chemical and physical states of the iron species.
Authors:T. Maruyama, D. Kaji, T. Kaneko, S. Goto, K. Tsukada, H. Haba, M. Asai, S. Ichikawa, Y. Nagame, and H. Kudo
Rapid chemical separation of berkelium is essential in order to measure the unknown isotope 252Bk. An anion exchange system of mineral acid and methanol was examined. An elution curve of Bk was obtained using 250Bk produced by the 248Cm+18O system and the 251Bk activity could be measured in the preliminary experiments. The whole chemical separation was completed within 30 minutes.